Polymerization of hydrocarbons



Nov. l2, 1940. LE ROY G. sTQRY POLYMERIZATION 0F HYDROCARBONS Filed sept'. 29, 1913"?L Patented Nov. l2, 194i) 2,221,171 K PoLYMERIzA'rIoN oF nYonocAmsoNs Le Roy G. Story, White Plains, N. Yaassgnor to The Texas Company, New York, Y., a corporation of Delaware v -application septenberzs, 1937, seria1No.1s6,279

ff 3 craintl This invention relates to the conversion of normally gaseous hydrocarbons into normally liquid hydrocarbons and has to do particularly with a process in which parailin hydrocarbons are converted into olefins and the resulting products subjected to polymerization in successive operations under the influence of heat and pressure and under the influence of an active polymerization catalyst.

In the polymerization of hydrocarbon gases containing parailns, it is often advantageous to crack the parains into oleflns and then subject the olens to polymerization. Such polymerization may be achieved by subjecting the oleflns to a lower temperature than the cracking operation and under a high pressure, and by contacting the olefins with an active catalyst of the phosphoric acid type. An advantageous method of operation is to rst subject the olen gases'to partial polymerization under the inuence of heat and pressure and then to further subject the unpolymerized olens to polymerization in the presence of an active catalyst to polymerize a further portion of the olens. comprises other features which will be understood from the following description read in connection with the accompanying drawing .which shows diagrammatically one form of apparatus for carrying out the process of the invention.

Referring to the drawing, a paraffinic charging stock which may be fresh charge introduced through the line I and pump 2, or recycle stock from the line 3, or a mixturev thereof, is forced under pressure through the heating coil 4 located in the furnace 5. The gases which may be undera pressure of 500-5000 pounds and preferably around 200G-3000 pounds, are heated to temperatures of about 1050 1250 F., and preferably around 1100 1250 F. The reaction time is intended to be only suicient to convert the parafns into a maximum amount of olens and may be about 1 5 minutes and preferably around 3 minutes or less. The reaction products are then reduced in temperature either by heat exchange o or by introduction of cooler gases through the line 8 into the transfer line 9. The products are introduced into the soaker or reaction drum I0, wherein polymerization is allowed to take place and a portion of the olefns is polymerizecl. Conditions maintained in the soaker may be about the pressures heretofore specified, and temperatures of 1000 F. or less, such as 800-1000 F. and preferably around 900 1000 F. The reaction time may vary from about 3 to 30 minutes, depending on the extent of the polymerization The invention desired. It is intended that sufficient polymerization takes place in the soakerto polymerize at least the more reactive components of the olens and may vary to the extent whereby the resulting polymer may be a heavy product in the nature of resinous or tarry material, or a liquid polymer containing a substantial amount of polymerization products from the more active olefins; for example, the polymerization products of the iso-butylene, such as di-isobutylene. The nature of the polymerization products resulting from this partial polymerization will also depend on the nature 'of the products subjected *o polymerization. It is desirable to obtain a product from `the cracking operation which will produceA The reaction products from the soaker III are transferred through the line I2 to fractionator I4. In the fractionator, the temperature is allowed to drop sufliciently to condense the desired amount of the normally liquid hydrocarbons. The extent of this condensation may vary from complete condensation of all normally liquid hydr'ocarbons to a partial condensation whereby only the higher boiling polymers, for example, those above 5 or 6 carbon atoms per molecule, are condensed. The liquid products so formed may be withdrawn from the lower portion of the fractionator through the valve controlled line I5, for use as a motor fuel or motor fuel blending reagent. The uncondensed vapors and gases are conducted from the upper portion of'the fractionator I4 through the vapor line I6 to a secondary fractionator I8 which is also maintained under high pressure. In this fractionator, the products may be vcooled whereby substantially all materials of higher number of carbon atoms than 2, and if desired substantially all the C2 hydrocarbons, are condensed and the permanent gases, such as hydrogen, methane and a portion or all of the C2 hydrocarbons are released from the top of the fractionator I8 through the valve controlled line I9. The liquid products collecting in the lower portion of the fractionator I8 are withdrawn through the line 2|) and the pressure thereon may be released through the valve 2| in the line 2li. It is preferable that the materials that are passed through the line are at suiciently high temperature so that when the pressure is released, substantially complete vaporization takes place. n some cases it may be desirable to eliminate the fractionator I8 and pass the products from fractionator I4 directly to the catalyst chamber 22.

5 An olefinic charging stock, such as cracked or other unsaturated gaseous hydrocarbons, is introduced through the line 2,5 and forced by the pump 26 through the line 21 to heat exchange coils 28 and 30, located in the fractionating towers I8 and I4 respectively. The olen charging stock so introduced may constitute the entire charging stock for the system or such charging stock may be supplemented or replaced by the paraffin charging stock referred to heretofore,

l5 introduced .through the line I. It is preferable when olenic charging stock is available to introduce the fresh charge through the line 25, whereby it is preheated in the coils 28 and 30 to temperatures of 3D0-600 F. and Ithen injected into the transfer line 9 by means of the line 8, referred to heretofore. A portion or all of the olenic charging stock may be introduced into the fractionator I4 through the by-pass line 32. One means of operation is to maintain a split stream whereby a portion is introduced into the fractionator I4 and the remainder injected into the transfer line 9. This charging stock is advantageously used by means of the preheater coils 28 and 30 and also by injection into the transfer 30 line 9, as'a means of controlling the temperatures in the system.

The unpolymerized gases and vapors passing through the line 20 are treated in the catalyst chamber 22 with an active polymerizing catalyst which is effective for polymerizing the less reactive olen's and, under suitable conditions, will effect substantially complete polymerization of the olens present. A catalyst which is suitable for this purpose is a phosphoric acid type of cata- 40 lyst and may be a calcined mixture of phosphoric acid and a solid adsorptive material, such as kieselguhr, fullers earth, diatomaceous earth, bentonite, etc. Such a catalyst may be one of the type disclosed in U. S. Patent 2,018,065 Ipatieif, October 22, 1935. Also liquid phosphoric acid may be used by means of liquid vapor contact or the phosphoric acid distributed on'nely divided material, such as silica. The treatment in the catalyst chamber 22 is preferably in the vapor phase at temperatures around 40G-500 F. Ordinarily the condensates withdrawn from the bottom of the fractionator I8 will beA of suflicient temperature that on releasing of pressure by means of the valve 2l, substantially complete vaporization takes place. A suitable pressure for operation in the catalyst tower 22 is around 100 pounds. conditions may be .varied so that the catalytic treatment may be partially or entirely in the co liquid phase.

The reaction. products are: withdrawn from the bottom of the tower 22 and passed through the transfer line 24 to a fractonator 35. In this fractionator, substantially complete condensation of the normally liquid hydrocarbons is effected. The liquid polymers, mainly of gasoline boiling range, are withdrawn from the bottom of the fractionator through the valve controlled. line 36. The unpolymerized gaseous hydrocarbons,

comprising mainly parafns, are conducted from the top of the fractionator 35 through the line .38 and recycled by means of the pump 29 and line 3, to the heating coil 4. Ordinarily this recycle stock will consist mainly of hydrocarbons of 3 and 4 carbon atoms per molecule, the lower It is to be understood, however, thatyC4 hydrocarbons are recycled.

As an example of the operation of the invention, an unsaturated gaseous hydrocarbon charg- 15 ing stock, such as cracked gases or gases separated from a cracking still, is preheated and commingled with the cracked gases discharged from a cracking coil in which parailln hydrocarbons are cracked. The proportions of materials and 20 the conditions ar-e maintained whereby the mixture may be subjected to reaction in a soaker at temperatures of about 900-1000 F. and pressures of about 2000-2500 pounds. A time of reaction around 10 to 20 minutes is allowed. The reac- 25 tion products are discharged into a fractionator and the polymer product separated consisting mainly of olenic hydrocarbons falling within the upper range of gasoline, and containing a substantial amount of Cs hydrocarbons. The 30 unpolymerized gases and vapors were further fractionated under high pressure whereby the hydrogen and methane and a portion of the C2 hydrocarbons were separated and released from the system as gases. The remaining products 35 were vaporized by reduction in pressure and the vapors contacted with a solid phosphoric acid type of catalyst at a temperature of about 450 F. and a pressure of around 100 pounds. The reaction products were discharged into a fraction- 40 ator wherein a polymer product was condensed and separated. This polymer comprised a large proportion of hydrocarbons of the lower boiling range of gasoline, which may be mixed with the primary polymer, referred to heretofore, to form 45 a blend having substantially commercial gasoline characteristics. The unpolymerized gases comprising C3 and C4 hydrocarbons and substantially of paraiiinic character, were recycled to the heating coil whereinthey were cracked 50 under pressures of about 2500 pounds and temperatures of around 1250 F. Extraneous charging stock, consisting mainly of propane and butane, was introduced into the heating coil in sufficient amounts to balance the operation, depend- 55 ing on the character, particularly with respect .to the unsaturation content, of the unsaturated gaseous charge. An ultimate lyield of about of gasoline having an antiknock value around was obtained. 60

An advantage of the process of the invention is the high conversion per pass and high ultimate yield, due in part to the substantially complete removal of the olens from the reaction products, whereby a recycle stock substantially entirely of 65 paraflnic character is obtained and which is subjected to the high temperature cracking operai tion. By avoiding the heating of olens in the cracking coil, the degradation and loss of the un- ,saturates are avoided. Also when carrying out 70 tive materials, whereby the load on the catalytic polymerization stage is relieved and a cleaner charge to the catalytic stage is obtained, whereby the active catalyst is less susceptible to poisoning and the life of the catalyst is materiall extended.

' Obviously many modications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof and therefore only such limitations should be imposed as are indicated in the appended claims. Iclaim:

1. A process for the conversion of normally gaseous hydrocarbons to normally liquid hydrocarbons, which comprises subjecting hydrocarbon gases containing paramn hydrocarbons of greater number of carbon atoms than one to temperatures suiicient to convert a substantial amount of said paraiiins to olens, subjecting the products of reaction to reaction at a lower temperature and a high pressure whereby a portion of the olens is polymerized to liquids, passing in heat exchange with the polymerization products charging 4stock containing olen hydrocarbons, thereafter commingling said charging stock with the products subjected to the polymerization operation, separating at least a portion of said liquids formed in the polymerization operation, sub- 40 gases containing paraffin hydrocarbons of greater number of carbon atoms than one to temperatures suiiicient to convert a substantial amount of said paraiiins to olens, subjecting the products of reaction to polymerization at a lower temperature and sufcient pressure to convert a portion of the olefin-s to normally liquid hydrocarbons, passing fresh charging stock in indirect heat exchange with the products from the polymerization operation thereby preheating the charge and condensing normally liquid hydrocarbons, commingling the preheated charge with the conversion products subjected to the polymerization operation, separating the condensed hydrocarbons, subjecting the uncondensed hydrocarbons .to catalytic polymerization whereby the remaining olefins are substantially polymerized, separating the resultant polymers and recycling the unpolymerized gases containing parain hydrocarbons to the rst mentioned conversion operation.

3. A process for the conversion of normally gaseous hydrocarbons to normally liquid hydrocarbons, which comprises subjecting hydrocarbon gases containing parain hydrocarbons of greater number of carbon atoms than one to temperatures suiiicient to convert a substantial amount of said parafns to oleiins, subjecting the products of reaction to polymerization at a lower temperature and suflicient pressure to convert a portion of the olens to normally liquid hydrocarlbons, passing fresh charging stock in indirect heat exchange with the products from the polymerization operation thereby preheating the charge and condensing normally liquid hydrocarbons, subjecting the uncondensed hydrocarbons to catalytic polymerization whereby the remaining olens are substantially polymerized, separating the polymers, recycling the unpolymerizedgases containing paraftn hydrocarbons to the iirst mentioned conversion operation, and cbmmingling a portion of said preheated charge with the gases subjected to the 'catalytic polymerization operation and another portion with the gases subjected to the thermal polymerization operation.

LE ROY G.- s'ronv.A 

